Zinc electrodes for batteries

ABSTRACT

An article having a continuous network of zinc and a continuous network of void space interpenetrating the zinc network. The zinc network is a fused, monolithic structure. A method of: providing an emulsion having a zinc powder and a liquid phase; drying the emulsion to form a sponge; annealing and/or sintering the sponge to form an annealed and/or sintered sponge; heating the annealed and/or sintered sponge in an oxidizing atmosphere to form an oxidized sponge having zinc oxide on the surface of the oxidized sponge; and electrochemically reducing the zinc oxide to form a zinc metal sponge.

This application is a continuation-in-part application of U.S. Pat. No. 9,802,254, issued on on Oct. 31, 2017. This application is also a continuation-in-part application of U.S. application Ser. No. 13/832,576, filed on Mar. 15, 2013, which claims the benefit of U.S. Provisional Application No. 61/730,946, filed on Nov. 28, 2012. These applications and all other publications and patent documents referred to throughout this nonprovisional application are incorporated herein by reference.

TECHNICAL FIELD

The present disclosure is generally related to porous zinc electrodes for use in batteries and other uses.

DESCRIPTION OF RELATED ART

The ongoing effort to fulfill the exigencies of ever-growing energy markets, including electric vehicles and portable electronic devices, has led to the investigation of battery technologies that promise to overcome some of the pitfalls of Li-ion batteries. While Li-ion batteries have the benefits of low self-discharge, no memory effect, and above all, rechargeability, the broader application of Li-ion-based energy storage is limited by safety concerns, manufacturing costs, and lower specific energy densities (<200 W h kg⁻¹) relative to other promising battery technologies (Lee et al., “Metal-air batteries with high energy density: Li-air versus Zn-air” Adv. Energy Mater. 2011, 1, 34-50). Zinc-air batteries, for example, have high practical specific energy densities (400 W h kg⁻¹) and the advantage of a cheap and environmentally friendly active material (zinc) coupled to air-breathing cathodes that consume molecular oxygen, which does not need to be stored within the battery (Neburchilov et al., “A review on air cathodes for zinc-air fuel cells” J. Power Sources 2010, 195, 1271-1291). While successful as a primary battery in certain commercial applications (e.g., the hearing-aid market), further utility of zinc-air is hindered by its limited rechargeability, lack of pulse power, and moderate utilization of theoretical discharge capacity (<60%). These limitations are inherent to the electrochemical behavior of zinc (Zn) in the traditional anode form-factors that are used in commercial zinc-air batteries.

When discharging a zinc-air battery containing zinc powder mixed with a gelling agent, electrolyte, and binders as the negative electrode, the metallic zinc is oxidized and reacts with the hydroxide ions of the electrolyte to form soluble zincate ions. The dissolved zincate ion diffuses from its point of electrogeneration until it reaches supersaturation conditions, and rapidly precipitates and dehydrates to form semiconducting zinc oxide (ZnO) (Cai et al., “Spectroelectrochemical studies on dissolution and passivation of zinc electrodes in alkaline solutions” J. Electrochem. Soc. 1996, 143, 2125-2131). Upon electrochemical recharge, the resultant zinc oxide is reduced back to zinc metal, albeit with a shape differing from the initial discharge. With increasing numbers of discharge-charge cycles, this shape change becomes more pronounced, eventually causing dendrites to grow from the negative electrode until they pierce the separator and cause electrical shorts that end battery operation.

BRIEF SUMMARY

Disclosed herein is an electrochemical cell comprising: an anode current collector; an anode in electrical contact with the anode current collector; an electrolyte; a cathode current collector; a cathode comprising silver or silver oxide in electrical contact with the anode current collector; and a separator between the anode and the cathode. The anode is made by a method comprising: providing a mixture comprising a metallic zinc powder and a liquid phase emulsion; drying the mixture to form a sponge; annealing and/or sintering the sponge in an inert atmosphere or under vacuum at a temperature below the melting point of zinc to form an annealed and/or sintered sponge having a metallic zinc surface; and heating the annealed and/or sintered sponge in an oxidizing atmosphere at a temperature above the melting point of zinc to form an oxidized sponge comprising a zinc oxide shell on the surface of the oxidized sponge. The anode comprises: a continuous network comprising metallic zinc; a continuous network of void space interpenetrating the zinc network; and metallic zinc bridges connecting metallic zinc particle cores. The electrolyte, fills the void space.

BRIEF DESCRIPTION OF THE DRAWINGS

A more complete appreciation of the invention will be readily obtained by reference to the following Description of the Example Embodiments and the accompanying drawings.

FIG. 1 shows a photograph (top) and scanning electron micrographs (middle and bottom) of a 3D zinc sponge after heating first in argon and then in air, showing the fused, through-connected porous network of the monolith and the surface structure of the individual particles within the sponge.

FIG. 2 shows a comparison of zinc sponges in the post-heated state (left: A,C,E) and after the electrochemical reduction step (right: B,D,F) as measured by (A,B) electrochemical impedance spectroscopy; (C,D) X-ray diffraction; and (E,F) scanning electron microscopy.

FIG. 3 shows (top) discharge potentials in a half-cell configuration at increasing applied currents, 5 mA-200 mA for 10-min increments and (bottom) linear dependence of the steady-state discharge voltage with increasing applied currents.

FIG. 4 shows (top) full-cell zinc-air battery demonstrations, prepared using the described zinc-sponge anodes and carbon/cryptomelane/Teflon® composite air-cathode and (bottom) discharge profiles of three zinc—air cells at discharge current densities of −5 mA cm⁻², 10 mA cm ⁻², and −24 mA cm⁻².

FIG. 5 shows (top) diagram of Zn/ZnO sponge symmetrical cell and (bottom) charge-discharge cycling data for up to 45 scans at an imposed load alternating between +24 mA cm ⁻² and −24 mA cm⁻².

FIG. 6 shows (top) SEM of a single particle of a fully reduced, all-metal zinc sponge and (bottom) SEM demonstrating the formation of a compact ZnO coating over the surface of the Zn sponge after charge/discharge cycling for 45 scans at ±24 mA cm⁻²; note that macroscale (>10 μm) dendrites are not observed.

FIG. 7 shows cell configuration of a high-power Ag—Zn prototype cell that comprises the Zn sponge anode.

FIG. 8 shows power cycling Ag—Zn cells using the Zn sponge electrode with applied currents ranging from 15-500 mA (˜15-500 mA cm²⁻; 0.2-5.6 A g⁻¹). The legend lists the plateaus in the same order from top to bottom.

FIG. 9 shows that silver-zinc cells comprising sponge anode achieve 96% of theoretical Zn utilization upon discharge (at 5.5 mA cm)and can be recharged to 97% of initial capacity (at 5.5 mA cm⁻²).

FIG. 10 schematically illustrates the effect of repeated cycling on the disclosed zinc structure.

FIG. 11 schematically illustrates the effect of repeated cycling on a prior art zinc structure.

DETAILED DESCRIPTION OF EXAMPLE EMBODIMENTS

In the following description, for purposes of explanation and not limitation, specific details are set forth in order to provide a thorough understanding of the present disclosure. However, it will be apparent to one skilled in the art that the present subject matter may be practiced in other embodiments that depart from these specific details. In other instances, detailed descriptions of well-known methods and devices are omitted so as to not obscure the present disclosure with unnecessary detail.

The fundamental requirements for zinc-containing secondary batteries are two-fold. In the case of zinc-air, the air-breathing cathode structure must contain catalysts for both the oxygen reduction reaction (ORR) for battery discharge and the oxygen evolution reaction (OER) for the reverse reaction upon recharge. The zinc anode composite requires either dendrite-inhibiting additives or its architecture must be designed so that the current density is uniformly distributed throughout the zinc structure, thereby decreasing the likelihood of dendrite formation and eventual shorting of the battery. This disclosure focuses on this re-design of zinc architectures to study the application for these zinc sponges to be used for secondary zinc-containing battery systems.

Disclosed herein is an approach to replace powdered-bed zinc anodes with highly porous, monolithic, and 3D through-connected zinc sponges as negative electrodes for use in current and to-be-developed high-performance zinc-containing batteries. In general, the zinc sponges are fabricated by forming a slurry of zinc powder in a two-phase mixture in the presence of emulsion stabilizers to produce highly viscous, yet pourable mixtures that are dried in molds and subsequently thermally treated to yield robust monolithic electrodes. The zinc sponges may exhibit high surface areas due to the interconnected pore network (sized at 10-75 μm), which may lead to an increase in achievable power density relative to commercial zinc-containing batteries. After an electrochemical reduction step, the device-ready electrode is interconnected in 3D, highly conductive, highly porous, infiltrated with electrolyte, structurally sound, and provides an ideal platform for use in rechargeable batteries that use zinc anodes or for primary batteries in which higher utilization of zinc is desired. The fully metallic sponge network provides an electronic environment of improved current distribution, thereby inhibiting the formation of dendrites that lead to electrical shorting. Preliminary characterization of the zinc sponge anode in flooded half-cell configurations is shown, as well as evaluations in full cell zinc-air battery prototypes, and demonstration of rechargeability without deleterious dendrite formation. U.S. Pat. Appl. Pub. No. 2016/0093890 is incorporated herein by reference, and all materials and methods disclosed therein are application to the presently disclosed subject matter.

Fully metallic, highly conductive pathways in 3D that allow for improved current distribution throughout the electrode structure precludes the discharge-charge cycles from having uneven reaction loci and high local current densities which spur formation of dendrites (Zhang, “Electrochemical thermodynamics and kinetics,” Corrosion and Electrochemistry of Zinc. 1996, 1^(st) Ed.; Arora et al,, “Battery separators” Chem Rev. 2004, 104, 4419-4462). In addition, a highly porous network of zinc allows for confined volume elements with high surface-to-electrolyte volume with faster concomitant saturation of zincate upon discharge and more rapid dehydration to ZnO, thereby minimizing shape change.

The electrode contains two bicontinuous interpenetrating networks. One is solid and comprises zinc and the other is void space. Thus the electrode is a porous zinc structure that may be in the form commonly referred to as a sponge. The zinc network may contain zinc on both the surfaces and the interior of the network. That is, it is not zinc coated onto a non-zinc porous substrate, and it may be pure or nearly pure zinc throughout. The zinc network may also comprise zinc oxide and/or zinc oxyhydroxides that form on the surface when the electrode is discharged in a cell. The zinc network is a fused, monolithic structure in three dimensions. The structure would not be made by merely pressing together zinc particles. Such a pressed material would not have the zinc particles fused together as the pressed particles could be separated from each other. The zinc network may have less than 5 wt. % zinc oxide or even less than 1 wt. %. A lower percentage of zinc oxide may result in better performance of the electrode, however since zinc can spontaneously oxidize in air, it may not be possible for the electrode to be completely zinc oxide-free.

As used herein, the void space refers to the volume within the structure that is not the zinc network nor any other material attached thereto. The void space may be filled with a gas or liquid, such as an electrolyte, and still be referred to as void space.

An example method for making the electrode begins with providing an emulsion of a zinc powder in a liquid phase. Any particle size of the zinc powder may be used, including but not limited to, 100 μm or less. Smaller particle sizes may result in better electrode performance. The liquid phase of the emulsion may be any liquid or mixtures thereof that can be evaporated and in which the zinc powder can be emulsified. A mixture of water and decane is one suitable liquid phase. The emulsification may be improved by the addition of an emulsifier and/or an emulsion stabilizer. One suitable emulsifier is sodium dodecyl sulfate and one suitable emulsion stabilizer is carboxymethylcellulose. Other such suitable emulsifiers and emulsion stabilizers are known in the art. The zinc metal may be alloyed with indium and bismuth or other dopants or emulsion additives that suppress gas evolution and corrosion of the sponge, which may improve performance of the electrode. The mixture of zinc and emulsion may have a viscosity of, for example 2-125 Pa·s, 2-75 Pa·s, or 50-125 Pa·s.

The zinc powder may be a blend of two or more different zinc powders having different average particle sizes. For example, a first zinc powder may have an average particle size in the range of 20-75 microns. A second zinc powder may have an average particle size in the range of 2-20 microns. Combinations of the two zinc powders will produce average pores per lineal inch representing the weighted contribution from both sources. When the multiple types of zinc powder are blended, a graph of the particle size distribution will exhibit at least two maxima. It is noted no portion of the zinc powder used to make the electrode should be omitted in such a particle size distribution. When all of the zinc in the emulsion is analyzed, there will be at least two maxima in the particle sizes. The use of multiple particle sizes can result in a higher volumetric density of zinc in the monolith and increased specific energy.

The emulsion is introduced into a container that defines the desired size and shape of the resulting Zn/ZnO monolith, and then dried to remove the liquid component. The dried emulsion yields a porous solid object comprising Zn/ZnO particles and void, herein designated as a “sponge”; this porous object may be fragile because the zinc powder particles are not fused together.

The mold may comprise a metal substrate, mesh, or foil (such as tin) or an alloyed substrate, mesh, or foil (such as tin-coated copper) capable of sustaining the temperatures reached in subsequent thermal treatment steps. This protocol yields electrodes that are metallically fused to another metal. Applications for this protocol include, but are not limited to, electronically connecting the sponge electrode to a current collector to be used in an electrochemical cell, such as a battery. In one procedure, the base of the mold is open and is placed over a metal mesh (tin-coated copper) with a mesh size through which the zinc particles cannot pass and comprising metals capable of sustaining the temperatures reached in (bottom) subsequent thermal treatment steps. The mesh may have an average opening size that is less than the d₅₀ particle size of the zinc powder.

Next the sponge is annealed and/or sintered under a low partial pressure of oxygen to form an annealed and/or sintered sponge. Such conditions may be found either in an inert atmosphere (examples could include argon or nitrogen flow) or under vacuum, all of which contain a trace amount of oxygen. The annealing and/or sintering is performed at temperature below the melting point of zinc and may be at least two thirds of the melting point of zinc. The temperature ramp may be, for example, 2° C./min and the dwell time may be for example, at least 30 minutes. The annealing and/or sintering fuses the zinc particles into a monolithic structure without causing enough melting to significantly change the overall morphology. The structure remains a sponge. Any annealing and/or sintering conditions that fuse the zinc particles together may be used. Example conditions include, but are not limited to, annealing and/ or sintering in argon at a peak temperature of 200 to 410° C. The fused structure contains metallic zinc with interconnecting bridges fusing the particles together.

Next, the annealed and/or sintered sponge is heated in an oxidizing atmosphere to produce zinc oxide on the surface of a partially oxidized sponge. The heating is done at a temperature above the melting point of zinc. This second heating step can improve the strength of the sponge for further handling, such as incorporation into a battery or other device. Since the zinc oxide does not melt and decomposes at a much higher temperature than the melting point of zinc, it preserves the sponge structure even at high temperatures. A zinc oxide shell covering the fused zinc network is formed, generally preserving the metallic zinc bridges and powder particle cores within the shell. Some or all of the bridges may be partially or entirely converted to zinc oxide, but the physical bridges are not destroyed. Within the zinc oxide shell, the metallic zinc may melt without altering the morphology of the sponge, while potentially further increasing the strength of the structure and the fusing bridges. Any heating conditions that form the zinc oxide may be used. Example conditions include, but are not limited to, heating in air at 420 to 650, 700° C., at least greater than the melting point of the zinc, or at least 150° C. greater than the melting point of the zinc for at least 30 minutes.

Next, the sponge is returned to the inert atmosphere at a temperature at or above the melting point of the metal, for example 420 to 650, 700° C., at least greater than the melting point of the zinc, or at least 150° C. greater than the melting point of the zinc for 30 min or longer. This third heating step can further improve the strength and interconnectivity of the sponge by terminating additional oxide formation and further fusing the metal core of the sponge backbone, while the shape is protected by the oxide formed on the surfaces in the previous step. The switch back to an inert atmosphere halts further conversion to zinc oxide, to maintain a high amount of zinc in the core.

Optionally, the zinc oxide is then electrochemically reduced back to zinc to form a zinc metal sponge. This sponge contains the interpenetrating zinc and void space networks. The reduction may take place after the electrode is placed in the device, such as a battery, for which it is intended. Any electrochemical conditions that reduce the zinc oxide may be used. It may be done, for example, by applying a negative voltage to the oxidized sponge until the open-circuit potential vs. zinc is less than 5 mV. As above, the fusing bridges are generally preserved and converted back to metallic zinc. Some amount of zinc oxide may be present on the surfaces of the zinc network, as some zinc will oxidize even at room temperature.

This structure differs from one made by a single heating step of heating a dried emulsion under vacuum at a high temperature above the melting point of zinc. Because the vacuum is not perfect and adventitious molecular oxygen will always be present, such heating would rapidly form a shell of zinc oxide on each individual zinc particle before metallic zinc bridges could form to fuse the particles together. Lacking these bridges, such a structure is highly fragile and may have less electrical interconnectedness than the presently disclosed structure.

The final electrode may be used in an electrochemical cell. Such a cell comprise an anode current collector, an anode comprising the zinc sponge electrode in electrical contact with an anode current collector, an electrolyte filling the void space, a cathode, a cathode current collector, and a separator between the anode and the cathode. The electrochemical cell may be a zinc-air, silver-zinc, or zinc-manganese oxide battery, or any other battery that includes a zinc electrode. The construction of such batteries is known in the art. When the anode of the cell is fully or partially discharged, zinc oxide and/or zinc oxyhydroxides may be formed on the surface of the zinc network.

FIG. 10 schematically illustrates the zinc sponge structure and the effect of repeated cycling. The top image shows a monolithic, aperiodic structure within which is a interconnected core of conductive metal throughout the three-dimensional (3D) volume of the sponge. As used herein “aperiodic” means that the structure does not conform to a regular or geometric pattern and is generally uniform throughout; in conjunction with the 3D-wired structure ensures a more uniform current distribution than other zinc powder formulations known in the art. All of the void space results from the same mechanism of drying the mixture. No other means, such as a template, for creating void spaces of a different size or type are used. The boundaries between the original zinc particles are not necessarily discernable. The structure is metallically interconnected in three dimensions. The lower view shows that upon discharge, all the surfaces of the Zn sponge structure are lined with zinc oxide. Recharging removes the zinc oxide and restores the structure to its essentially all-metal form. This cycling may be repeated many times without forming macroscale dendrites, as described in Parker et al., Science, 356, 415-418 (2007) (incorporated herein by reference).

The aperiodic structure may be formed by the natural packing of the metallic zinc powder upon sedimentation of a well-mixed emulsion (containing well-dispersed zinc particles) during slow evaporation of the emulsifying liquids to create a consolidated, fragile, molded form-factor. After removal from the mold, annealing the consolidated, mold-free void-solid shape at a temperature just below the melting point of the original metallic powder in a non-oxidizing atmosphere ensures that particle-to-particle atomic-scale bridges form as the organic components of the original emulsion are thermally decomposed to volatile species and thereby removed from the void-solid structure of the monolithic object consolidated from the original emulsion. Calcining the annealed void-solid shape in an oxidizing atmosphere at 650° C., a temperature several hundred degrees Celsius above the melting point of the original metallic zinc powder, ensures that the inner metallic zinc melts and flows while the void-solid structure of the annealed void-solid shape is captured by a hard shell of zinc oxide at the annealed solid network, which maintains the annealed porous structure by preventing collapse or sinking of the oxide-coated solid network into the void. The general size of the void network in the final porous monolithic form-factor may be established by the size of the particles used to make the zinc emulsion. This can produce pore diameters of 1-100 microns and pores per lineal inch of 160-6000 or specifically an average greater than 300 pores per lineal inch. The first zinc powder may produce regions of average pores per lineal inch in the range of 169-635. The second zinc powder produce regions with average pore per lineal inch in the range of 635-6350. Combinations of the two zinc powders will produce average pores per lineal inch representing the weighted contribution from both sources.

FIG. 11 schematically illustrates an example of prior art zinc structure and the effect of repeated cycling. The ad hoc nature of zinc powders loosely bound together, often with binders and gelling agents, results in a nonuniform current distribution. The lower view shows that repeated discharging and recharging produces nonuniform formation of zinc oxide and therefore nonuniform regeneration of zinc upon charging. A portion of the structure that contains zinc oxide after discharging, may no longer be connected to the circuit, such that the load of the battery is directed to narrow regions, which may result in the formation of zinc dendrites (McBreen, “Rechargeable Zinc Batteries” J. Electroanal. Chem. 1980, 168, 415-432).

Other prior art zinc structures may be made using a porous polymeric foam as a template (e.g., Arrance, U.S. Pat. No. 3,287,166). The template is filled with the slurry and combusted away, such that what was void in the original template becomes solid. What was solid in the template becomes large scale voids. The large voids may be on the order of a millimeter in diameter, with overall pores per lineal inch less than 50.

Other possible applications include the use of the zinc sponges in a variety of battery systems containing zinc as the negative electrode. Full-cell batteries (e.g., silver-zinc, nickel-zinc, zinc-carbon, zinc-air, etc.) can be prepared without modification of the fabrication procedure of the zinc sponges described herein, with or without electrolyte additives. The full-cell batteries described herein may utilize a nylon screw cap as the cell holder. Alternatives to this include any cell holder that contains zinc as an electrode component. Other alternatives include fabrication procedures designed to yield 3D, through-connected zinc structures, in an effort to produce porous zinc monoliths with uniform current distribution as a means to suppress dendrite formation, enhance cyclability, and/or increase zinc utilization in primary or secondary zinc-containing batteries.

A suitable electrolyte is a KOH. Any amounts and concentration that result in a functional cell may be used.

The development of zinc-containing batteries, capable of high-power operation and enhanced rechargeability requires a redesign of the architecture of the zinc electrode to provide high-surface-area electrochemical interfaces and to support improved current distribution to thereby suppress the overgrowth of electrodeposited Zn and deleterious dendrite formation. Traditional powdered-bed zinc composites predominantly used as negative electrodes in commercial zinc-containing batteries (e.g., zinc air) suffer from low utilization (<60%) of theoretical specific capacity of Zn, high content of electrolyte additives, nonuniform current distribution, and limited rechargeability. The electrode disclosed herein describes the preparation of new zinc anodes that markedly improve on these drawbacks.

The formation of zinc powder emulsions with subsequent two-step annealing and/or sintering and electrochemical reduction steps yields robust, scalable, monolithic zinc sponges that are device-ready for a variety of zinc-containing batteries. The resultant zinc sponge comprises two interpenetrating, co-continuous networks of zinc metal and void, which improves current distribution throughout the structure of the electrode. This feature, inherent to the 3D architecture of the anode, hinders the formation of concentration gradients that would otherwise lead to disproportionate reaction centers that encourage growth of dendrites that inevitably cause battery shortage. The primary zinc-air battery used in the example below utilizes >20% more zinc than commercial powdered-bed zinc anode composites thereby providing higher specific energy, another feature expected from a metallic network of improved current distribution. In addition, a highly porous network co-continuous with the network of zinc metal allows for confined volume elements with high ratios of surface-to-electrolyte-volume that promote faster saturation of zincate upon discharge and more rapid dehydration to ZnO, thereby minimizing shape change. This notion, coupled with the dendrite suppression resulting from improved current distribution allows for rechargeability not seen with the Zn anodes in commercial zinc-air batteries.

The following examples are given to illustrate specific applications. These specific examples are not intended to limit the scope of the disclosure in this application.

EXAMPLE 1 Fabrication of Monolithic Zinc Sponges

A typical preparation of zinc sponge electrodes begins with the formation of an emulsion of zinc powder in water and decane. In a small beaker or scintillation vial, 6.0 g of zinc powder that also contains 300-ppm indium and 285-ppm bismuth (as-received from Grillo-Werke AG) was added. The indium and bismuth additives are necessary to raise the overpotential for hydrogen evolution in alkaline electrolytes, while eliminating the need for toxic additives such as lead and mercury (Glaeser, U.S. Pat. No. 5,240,793). Water (1.027 mL) and decane (2.282 mL) were added along with an emulsifier, sodium dodecyl sulfate (6.3 mg) and emulsion stabilizer, carboxymethylcellulose (0.253 g). The use of these ingredients in the formation of zinc emulsions that are subsequently used to make zinc electrodes has been described previously (Drillet et al., “Development of a Novel Zinc/Air Fuel Cell with a Zn Foam Anode, a PVA/KOH Membrane, and a MnO₂/SiOC-based Air Cathode” ECS Trans. 2010, 28, 13-24). The mixture was stirred rapidly at a rate of 1,200 rpm for >15 min to insure complete uptake of zinc into the emulsion. The freely flowing, yet viscous emulsion was poured into cylindrical, polyethylene molds and allowed to air-dry overnight. The molds used in this example were 1.15-cm in diameter and could yield zinc sponges front 1-4 mm thick; however, this procedure is scalable to other sizes and shapes. After 16-24 hours of drying, the mold was inverted to release the zinc monoliths, which were fragile at this stage. To strengthen the zinc sponges, samples were transferred to a tube furnace and heated under flowing argon at a positive ramp rate of 2° C. min⁻¹ to an annealing temperature of 400° C. and held for 2 h. The argon flow was then removed and the tube was opened to ambient air and heated for a second step at 2° C. min⁻¹ to 650° C. and held for 2 h. This final step encapsulates the surface of the annealed zinc particles with a shell of ZnO needles, which is necessary to impart additional strengthening character to the zinc sponges. After 2 h, the tube was allowed to cool without any rate control. The resultant monolith was characterized with scanning electron microscopy (SEM) as seen in FIG. 1.

EXAMPLE 2 Zinc Sponges as a Negative Electrode in Zinc-Air Batteries

The intentional introduction of oxide to the zinc sponges enhances the mechanical integrity, allowing them to be routinely handled with decreased risk of fracture; however, a layer of oxide on the zinc lowers the initial capacity upon discharge and introduces contact resistance when assembling the zinc-containing cell (see Nyquist plots from electrochemical impedance spectroscopy (EIS) in FIG. 2A). In order to electrochemically reduce the ZnO coating, the sponge is used as part of the working electrode in a half-cell, three-electrode configuration with a Pt counter electrode and zinc quasi-reference electrode in 6 M KOH. A zinc sponge was placed in an envelope of tin-coated-copper mesh to form the working electrode. (Tin contacts were used because tin is galvanically compatible with zinc and corrosion of the electrode is suppressed that would otherwise be rampant with other current collectors (e.g., nickel, copper, etc.).) In a typical experimental sequence, the open-circuit potential (OCP) of the cell was measured versus a metallic zinc quasi-reference electrode, and then an initial EIS measurement was performed. The initial OCP typically exceeded 40 mV vs. Zn, and the real impedance (R_(CT)) was much higher than that expected for metallic contact, consistent with the presence of a poorly conducting zinc oxide coating on the zinc sponge. Electrochemical reduction of the oxide-coated sponge to its metallic zinc counterpart was achieved by applying a constant potential of −50 mV for 30 min, followed by additional EIS and OCP measurements. This sequence was repeated until the open-circuit potential was stable at or near 0 mV, indicating complete reduction to zinc metal. The charge-transfer resistance decreased to less than 0.2 Ωcm⁻² for the electroreduced zinc sponge, as compared to the post-heated zinc sponge, where resistance exceeded 60 Ωcm⁻² (FIGS. 2A,B). Conversion of ZnO to Zn metal was confirmed using X-ray diffraction (Rigaku, FIGS. 2C, 2D), which showed a loss of the ZnO reflections, leaving only metallic zinc after electroreduction. In addition, after reduction there was no obvious loss in the porosity or mechanical strength of the zinc monoliths; however, a measureable mass loss was recorded, due to oxygen mass lost as ZnO is reduced to Zn as well as some corrosion of zinc to form soluble products that are lost to the alkaline electrolyte. Based on twelve control experiments, using zinc sponges annealed and oxidized using the thermal treatment described above, the average mass loss associated with this electrochemical reduction step is 23.9±3.4%. FIGS. 2E, 2F highlight the changing morphology after the reduction step, effectively removing the shell of zinc oxide associated with the as-prepared sponges.

The reduction step described above successfully lowered the amount of zinc oxide present in the sponge, which would otherwise limit capacity and increase resistance when incorporated into a zinc-containing battery. The half-cell testing configuration provides a quality check on the impedance characteristics of the anode prior to use in full-cell batteries, but it can also be a useful tool to study the power capabilities of zinc sponges as anodes. For example, a zinc monolithic sponge (1.15-cm diameter; 3.5-mm thick) was attached to a tin current collector with LOCTITE® Hysol® 1C™ epoxy completely surrounding all components except for the face of the zinc sponge. A reducing voltage of −50 mV versus zinc was applied for 50 min followed by discharging (i.e., oxidizing) the zinc sponge at constant current (5 mA) for 10 min to measure the steady-state discharge voltage. This protocol was repeated with increasing applied currents as shown in FIG. 3. The galvanostatic experiments revealed a linear dependence of the steady-state discharge voltage on applied current. Even at an imposed current of 200 mA (193 mA cm⁻²) the overpotential required for maintaining this current density was only 230 mV. The ability to maintain low overpotentials even at high load (current density) is an enabling characteristic of the zinc sponge architecture. Conventional zinc-containing batteries, including zinc-air, typically operate with up to a 500 mV drop with respect to open-circuit voltage (Linden, “Zinc/air cells” Handbook of Batteries. 1984, 2^(nd) Ed.).

Once the zinc sponge was fully reduced to Zn⁰, it was ready to be used as a negative electrode in a full-cell battery. The prototype zinc-air cell used for preliminary testing is based on a 1.8-cm nylon screw cover (Hillman Group), which snaps together with a 6-mm hole on the top face, which serves as the air-breathing side of the cell. A platinum wire was attached to a tin current collector and used as the negative terminal during battery testing. Following the separate electrochemical reduction step, the zinc sponge, still infiltrated with a 6 M KOH, was submerged in a gel electrolyte synthesized from 6 g of polyacrylic acid dissolved in 100 mL of 6 M KOH. To prepare the full Zn-air cell, excess gel was dabbed away from the gel-dipped zinc sponge, leaving only a thin coating. The viscous gel electrolyte insures the zinc sponge remains fully infiltrated with liquid electrolyte while slowing the evaporation of solvent. The zinc sponge was placed on the tin current collector, and then topped with an aqueous-compatible separator with dimensions slightly larger than the diameter of the zinc sponge (1.15 cm). The positive electrode terminal comprises an air-cathode composite of Ketjen black carbon, cryptomelane, and Teflon® attached to a piece of nickel mesh, attached to a platinum wire lead. The results of typical zinc-air full cells utilizing these zinc sponge anodes are shown in FIG. 4. In these examples, all initial OCPs were measured above 1.4 V prior to discharging the full cells at −5.0, −10, and −24 mA cm⁻². The average discharge voltage for these cells was 1.25, 1.19, and 1.13 V, respectively, each with a cutoff voltage of 0.9 V. The corresponding specific capacity obtained at the −5, −10, and −24 mA cm⁻² discharges were 728, 682, and 709 mAh g_(Zn) ⁻¹ with respective specific energy densities of 907, 834, and 816 Wh kg_(Zn) ⁻¹ and corresponding zinc utilization for these cells of 89%, 83%, and 86%. These metrics are an improvement over standard commercial zinc-powder composite anodes, which generally only utilize 50-60% of the theoretical specific capacity of zinc (Zhang, “Fibrous zinc anodes for high power batteries.” J Power Sources. 2006, 163, 591).

EXAMPLE 3 Reversibility of Zinc Sponge Anodes

In order to study the reversibility of the 3D zinc sponge in a battery configuration, without the requirement of having an optimized cathode (e.g., bifunctionally catalytic for the ORR or OER), a symmetrical electrochemical cell containing an all-metal Zn sponge versus a Zn/ZnO sponge separated by an aqueous-compatible separator was used. The Zn/ZnO sponge was prepared by electroreducing some of the ZnO present from the post-heated sponge by applying −50 mV versus zinc for 10-min increments. The EIS and the OCP were measured after each cycle. The reduction of this sponge was terminated when the R_(CT) in the EIS fell below 0.5 Ωcm⁻², but the OCP remained greater than 30 mV vs. Zn, indicating high conductivity throughout the sponge network, yet ZnO remained. A second post-heated sponge was reduced at −50 mV versus Zn for 30-min increments as described in Example 2 until it was fully reduced to all metal Zn sponge with an OCP very close to 0 mV vs. Zn. For the construction of the symmetrical cell, the negative electrode was an all-metal Zn sponge in electrical contact with a tin foil current collector and the positive electrode was the Zn/ZnO sponge electrode, also in contact with a tin foil current collector. Both sponge electrodes were pre-infiltrated with 6 M KOH and were separated by an aqueous-compatible separator (see FIG. 5). For the first step in the evaluation of the symmetrical cell, −24 mA cm⁻² was applied for 1 h to reduce some of the ZnO in the Zn/ZnO sponge, which is coupled to the oxidation of Zn in the opposing sponge. Then +24 mA cm⁻² was applied in the second step to initiate the reverse reactions. The full symmetrical cell was cycled at ±24 mA cm⁻² until one of the steps crossed the ±100 mV threshold. No electrical shorts were observed. For this example, the symmetrical cell was cycled for 45 charge-discharge cycles at a depth-of-discharge of ˜23%. For post-cycling analysis, the electrodes were removed from the cell, rinsed thoroughly, and dried in vacuo overnight. Scanning electron micrographs show that the sponges maintained their porosity post-cycling (FIG. 6). In addition, no obvious signs of shape change, dendrite formation, or nonuniform deposition were observed. The cycling of the zinc sponges resulted in a compact layer of zinc or zinc oxide on the surface of the particles of the monolith rather than flowery dendrites, demonstrating an increase in cyclability that is a result of this well-wired, well-plumbed zinc sponge architecture.

EXAMPLE 4 Fabrication of Monolithic Zinc Sponges with Increased Volumetric Density

An example preparation of zinc (Zn) sponge electrodes with higher volumetric density (179-2.14 g cm⁻³) began with the formation of an emulsion of Zn powder in water and decane. In a small container, an emulsifier (sodium dodecyl sulfate, 21 mg) and emulsion stabilizer (carboxymethylcellulose, 0.844 g) were added to a stirring mixture of de-ionized water (2.054 mL) and decane (4.565 mL) and stirred for 10 min at 300 rpm. To this mixture, Zn metal powder (20 g) was added. The powder in this example was a mixture comprising Zn particles from two sources: (i) Zn powder with an average particle diameter of ˜50 μm which contains 300-ppm indium and 300-ppm bismuth; and (ii) Zn powder with an average particle diameter <20 μm and contains 200-ppm indium and 200-ppm bismuth. For the Zn sponges prepared in this example, the large particles comprised 30 wt. % of the powder mixture while the small particles comprised the remaining 70 wt. %, but other ratios may be used. The indium and bismuth additives are introduced by the manufacturer and serve to lower the overpotential for hydrogen evolution in alkaline electrolytes, while eliminating the need for toxic additives such as lead and mercury (Glaeser, U.S. Pat. No. 5,240,793). After the Zn was added to the stirring oil/water mixture, the stirring rate was slowly increased to 1,200 rpm and stirred for at least 15 min at 1,200 rpm to insure complete uptake of Zn powder into the emulsion. The freely flowing, yet viscous emulsion was pipetted in 0.5 mL aliquots into 1.15-cm diameter polyethylene molds and allowed to sit and dry overnight under ambient atmosphere and temperature for, in this example, 16 h. After drying, the mold was inverted to release the Zn monolith; the released Zn forms were fragile at this stage. To strengthen the zinc sponge, samples were transferred to a tube furnace and heated under a flowing inert gas (e.g., argon) at a positive ramp rate of 2° C. min⁻¹ to an annealing temperature of 410° C. and held for 2 h (m.p._(Zn)=419.5° C.) The inerting flow was then removed, the tube opened to ambient air, and then in a second step heated in static air at 2° C. min⁻¹ to 665° C. and held for 2 h. This step encapsulated the surface of the annealed Zn particulate framework with a shell of thermally grown ZnO, which imparts additional strengthening character to the Zn sponges. After 2 h the tube was allowed to cool without any rate control. The resultant monoliths have a volumetric density that ranges from 1.79-2.14 g cm⁻³ (or 25-30% dense with respect to nonporous Zn metal), and are thus termed “Zn30” herein.

EXAMPLE 5 Zinc Sponges as a Negative Electrode in High-Power Silver-Zinc Batteries

Following the electrochemical reduction step to convert a thermally treated Zn sponge to the metallic Zn⁰ analog, the Zn sponge of Example 4 was thoroughly rinsed with deionized water, dried, and re-weighed in order to get an accurate assessment of Zn active material capacity before prototype testing. The ˜1-cm² reduced Zn sponge was infiltrated with 6 M KOH, placed atop a tin current collector, and then topped with four separators: a microporous (e.g., Celgard 3501), two layers of CELLOPHANE®, and one layer of a nonwoven (e.g., Freudenberg 700/28K). The CELLOPHANE® and nonwoven separators were also infiltrated with the 6 M KOH electrolyte prior to cell assembly. The positive electrode terminal comprised a silver oxide (Ag_(x)O) cathode in mechanical contact with a piece of Pt or Ag foil attached to a platinum wire. The Ag_(x)O cathode was made by pressing Ag_(x)O (0.5 g) into a Ag mesh (in a 1-cm pellet die set) to 7,000 psi. All cell materials were housed in a 1.8-cm nylon screw cover (Hillman Group). An expanded view of the cell assembly is shown in FIG. 7.

The prototype Ag—Zn cells for this example were prepared to demonstrate the power capabilities of the Zn sponge, although Ag—Zn cells that use a Zn sponge anode could also be used for rechargeable applications. In this example, the open-circuit voltage was measured as ˜1.66 V prior to discharging the Ag—Zn cells at 15, 25, 50, 100, 200, 300, 400, and 500 mA. (˜15-500 mA cm⁻², corresponding to mass-normalized values of 0.2-5.6 A g⁻¹). The lower voltage limit for the example cell of FIG. 8 was set at 1.0 V, and was never reached for the current density range examined indicating no power limitation at the specified loads. The total specific capacity of the eight power excursion sums to a total of 246 mA g_(Zn) ⁻¹, equivalent to 30% depth-of-discharge with respect to the total amount of theoretical Zn active material present, highlighting that each power step shown in this example is of a sustained, continuous load, rather than sub-second pulses. The corresponding specific power (current×average voltage) delivered by the cell ranges from 260-5,800 W kg_(Zn) ⁻¹, depending on the applied current density. In packaged and optimized Ag—Zn cells, assuming 20% of the cell contains a Zn sponge anode, the specific power would equate to ˜50-1,200 W kg⁻¹, depending on the applied current density.

EXAMPLE 6 Zinc Sponges as a Negative Electrode in High Capacity Rechargeable Silver-Zinc Batteries

Following the electrochemical reduction step to convert a thermally treated Zn sponge to the metallic Zn⁰ analog, the Zn sponge of Example 4 was thoroughly rinsed with deionized water, dried, and re-weighed in order to get an accurate assessment of Zn active material capacity before prototype testing. The total mass of the ˜1-cm² reduced Zn sponge used for this example was 0.101 g. Once infiltrated with the 6 M KOH electrolyte, the Ag—Zn cell was constructed according to the previous example. The ability of Zn sponge anodes to discharge to high Zn mass-normalized capacity and be recharged without inducing dendritic shorts was probed by exhaustively discharging Ag—Zn cells (FIG. 9) at a current density of ˜5.5 mA cm⁻² (C/15) and then recharging at the same rate. The cell discharged with an average voltage of 1.50 V and reached 96% DOD_(Zn) (787 mA h g_(Zn) ⁻¹; 1181 W h kg_(Zn) ⁻¹) and could be recharged to 97% capacity from this extreme depth. No dendritic shorts were observed.

Obviously, many modifications and variations are possible in light of the above teachings. It is therefore to be understood that the claimed subject matter may be practiced otherwise than as specifically described. Any reference to claim elements in the singular, e.g., using the articles “a,” “an,” “the,” or “said” is not construed as limiting the element to the singular. 

What is claimed is:
 1. An article comprising; a continuous network comprising metallic zinc; and a continuous network of void space interpenetrating the zinc network; wherein the zinc network comprises a fused, monolithic structure; wherein the article comprises metallic zinc bridges connecting metallic zinc particle cores; and wherein the article is made by: providing a mixture comprising a metallic zinc powder and a liquid phase emulsion; wherein the particle size distribution of all of the metallic zinc powder used to make the article has two maxima; drying the mixture to form a sponge; sintering the sponge in an inert atmosphere or under vacuum at a temperature below the melting point of zinc to form a sintered sponge having a metallic zinc surface; and heating the sintered sponge in an oxidizing atmosphere at a temperature above the melting point of zinc to form a zinc oxide shell on the surface of the sintered sponge.
 2. The article of claim 1, wherein both the surface of the zinc network and the interior of the zinc network comprise zinc.
 3. The article of claim 1, wherein the surface of the zinc network comprises one or more of zinc oxide and zinc oxide oxyhydroxides.
 4. The article of claim 1, wherein the zinc network is substantially uniformly conductive.
 5. The article of claim 1, wherein the inert atmosphere is argon or nitrogen.
 6. The article of claim 1, wherein the article is further made by: reducing the zinc oxide.
 7. The article of claim 1, wherein the void space comprises 10-75 micron-sized pores.
 8. The article of claim 1; wherein one of the two maxima is in a range of 2-20 microns; and wherein the other of the two maxima is in a range of 20-75 microns.
 9. An electrochemical cell comprising: an anode current collector; an anode comprising the article of claim 1 in electrical contact with the anode current collector; an electrolyte filling the void space; a cathode current collector; a cathode in electrical contact with the anode current collector; and a separator between the anode and the cathode.
 10. The electrochemical cell of claim 9, wherein the electrochemical cell is a zinc-air battery.
 11. The electrochemical cell of claim 9, wherein the anode can be oxidized and reduced for at least 45 cycles without the formation of zinc dendrites.
 12. A method comprising: providing a mixture comprising a metallic zinc powder and a liquid phase emulsion; wherein the particle size distribution of all of the metallic zinc powder used to make the article has two maxima; drying the mixture to form a sponge; sintering the sponge at a temperature below the melting point of zinc to form a sintered sponge; and heating the sintered sponge in an oxidizing atmosphere at a temperature above the melting point of zinc to form a zinc oxide shell on the surface of the sintered sponge.
 13. The method of claim 12, wherein the liquid phase emulsion comprises water and decane.
 14. The method of claim 2, wherein the emulsion comprises an emulsifier and an emulsion stabilizer.
 15. The method of claim 14, wherein the emulsifier is sodium dodecyl sulfate and emulsion stabilizer is carboxymethylcellulose.
 16. The method of claim 12; wherein one of the two maxima is in a range of 2-20 microns; and wherein the other of the two maxima is in a range of 20-75 microns.
 17. The method of claim 12, wherein the sintering is performed under argon at a peak temperature of 200-410° C.
 18. The method of claim 12, wherein the heating is performed in air at a peak temperature greater than 420° C.
 19. The method of claim 12, wherein the sintering is performed in an inert atmosphere or under vacuum; and wherein the sintered sponge has a metallic zinc surface.
 20. The method of claim 19, the inert atmosphere is argon or nitrogen.
 21. The method of claim 12, further comprising: reducing the zinc oxide.
 22. The method of claim 21, wherein the zinc oxide is reduced by applying a negative voltage to the oxidized sponge until the open-circuit potential vs, zinc is less than 5 mV.
 23. An electrochemical cell comprising: an anode current collector; an anode in electrical contact with the anode current collector; wherein the anode is made by a method comprising: providing a mixture comprising a metallic zinc powder and a liquid phase emulsion; drying the mixture to form a sponge; annealing and/or sintering the sponge in an inert atmosphere or under vacuum at a temperature below the melting point of zinc to form an annealed sponge having a metallic zinc surface; and heating the annealed sponge in an oxidizing atmosphere at a temperature above the melting point of zinc to form an oxidized sponge comprising a zinc oxide shell on the surface of the oxidized sponge; wherein the anode comprises: a continuous network comprising metallic zinc; a continuous network of void space interpenetrating the zinc network; and metallic zinc bridges connecting metallic zinc particle cores; an electrolyte filling the void space; a cathode current collector; a cathode comprising carbon; and a separator between the anode and the cathode.
 24. An article made by method comprising: providing a mixture comprising a zinc powder and a liquid phase emulsion; drying the emulsion to form a sponge; sintering the sponge in an inert atmosphere to form a sintered sponge; heating the sintered sponge in an oxidizing atmosphere to form an oxidized sponge comprising zinc oxide on the surface of the oxidized sponge; and heating the oxidized sponge in an inert atmosphere at above the melting, point of the zinc. 